The role of the [CpM(CO)2]- chromophore in the optical properties of the [Cp2ThMCp(CO)2]+ complexes, where M = Fe, Ru and Os. A theoretical view

Plinio Cantero-López; Laura Le Bras; Dayán Páez-Hernández; Ramiro Arratia-Pérez

doi:10.1039/c5dt03121d

The role of the [CpM(CO)₂]^- chromophore in the optical properties of the [Cp₂ThMCp(CO)₂]⁺ complexes, where M = Fe, Ru and Os. A theoretical view

Plinio Cantero-López, Laura Le Bras, Dayán Páez-Hernández, Ramiro Arratia-Pérez

Facultad Ciencias Exactas

Producción científica: Contribución a una revista › Artículo › revisión exhaustiva

18 Citas (Scopus)

Resumen

The chemical bond between actinide and the transition metal unsupported by bridging ligands is not well characterized. In this paper we study the electronic properties, bonding nature and optical spectra in a family of [Cp₂ThMCp(CO)₂]⁺ complexes where M = Fe, Ru, Os, based on the relativistic two component density functional theory calculations. The Morokuma-Ziegler energy decomposition analysis shows an important ionic contribution in the Th-M interaction with around 25% of covalent character. Clearly, charge transfer occurs on Th-M bond formation, however the orbital term most likely represents a strong charge rearrangement in the fragments due to the interaction. Finally the spin-orbit-ZORA calculation shows the possible NIR emission induced by the [FeCp(CO)₂]^- chromophore accomplishing the antenna effect that justifies the sensitization of the actinide complexes.

Idioma original	Inglés
Páginas (desde-hasta)	20004-20010
Número de páginas	7
Publicación	Dalton Transactions
Volumen	44
N.º	46
DOI	https://doi.org/10.1039/c5dt03121d
Estado	Publicada - 2015

Áreas temáticas de ASJC Scopus

Química inorgánica

Acceder al documento

10.1039/c5dt03121d

Otros archivos y enlaces

Enlace a la publicación en Scopus

Citar esto

@article{5c038d002f144008af12ec29c4ac87f2,

title = "The role of the [CpM(CO)2]- chromophore in the optical properties of the [Cp2ThMCp(CO)2]+ complexes, where M = Fe, Ru and Os. A theoretical view",

abstract = "The chemical bond between actinide and the transition metal unsupported by bridging ligands is not well characterized. In this paper we study the electronic properties, bonding nature and optical spectra in a family of [Cp2ThMCp(CO)2]+ complexes where M = Fe, Ru, Os, based on the relativistic two component density functional theory calculations. The Morokuma-Ziegler energy decomposition analysis shows an important ionic contribution in the Th-M interaction with around 25% of covalent character. Clearly, charge transfer occurs on Th-M bond formation, however the orbital term most likely represents a strong charge rearrangement in the fragments due to the interaction. Finally the spin-orbit-ZORA calculation shows the possible NIR emission induced by the [FeCp(CO)2]- chromophore accomplishing the antenna effect that justifies the sensitization of the actinide complexes.",

author = "Plinio Cantero-L{\'o}pez and {Le Bras}, Laura and Day{\'a}n P{\'a}ez-Hern{\'a}ndez and Ramiro Arratia-P{\'e}rez",

note = "Publisher Copyright: {\textcopyright} The Royal Society of Chemistry 2015.",

year = "2015",

doi = "10.1039/c5dt03121d",

language = "English",

volume = "44",

pages = "20004--20010",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "46",

}

The role of the [CpM(CO)₂]^- chromophore in the optical properties of the [Cp₂ThMCp(CO)₂]⁺ complexes, where M = Fe, Ru and Os. A theoretical view. / Cantero-López, Plinio; Le Bras, Laura; Páez-Hernández, Dayán et al.
En: Dalton Transactions, Vol. 44, N.º 46, 2015, p. 20004-20010.

Producción científica: Contribución a una revista › Artículo › revisión exhaustiva

TY - JOUR

T1 - The role of the [CpM(CO)2]- chromophore in the optical properties of the [Cp2ThMCp(CO)2]+ complexes, where M = Fe, Ru and Os. A theoretical view

AU - Cantero-López, Plinio

AU - Le Bras, Laura

AU - Páez-Hernández, Dayán

AU - Arratia-Pérez, Ramiro

PY - 2015

Y1 - 2015

N2 - The chemical bond between actinide and the transition metal unsupported by bridging ligands is not well characterized. In this paper we study the electronic properties, bonding nature and optical spectra in a family of [Cp2ThMCp(CO)2]+ complexes where M = Fe, Ru, Os, based on the relativistic two component density functional theory calculations. The Morokuma-Ziegler energy decomposition analysis shows an important ionic contribution in the Th-M interaction with around 25% of covalent character. Clearly, charge transfer occurs on Th-M bond formation, however the orbital term most likely represents a strong charge rearrangement in the fragments due to the interaction. Finally the spin-orbit-ZORA calculation shows the possible NIR emission induced by the [FeCp(CO)2]- chromophore accomplishing the antenna effect that justifies the sensitization of the actinide complexes.

AB - The chemical bond between actinide and the transition metal unsupported by bridging ligands is not well characterized. In this paper we study the electronic properties, bonding nature and optical spectra in a family of [Cp2ThMCp(CO)2]+ complexes where M = Fe, Ru, Os, based on the relativistic two component density functional theory calculations. The Morokuma-Ziegler energy decomposition analysis shows an important ionic contribution in the Th-M interaction with around 25% of covalent character. Clearly, charge transfer occurs on Th-M bond formation, however the orbital term most likely represents a strong charge rearrangement in the fragments due to the interaction. Finally the spin-orbit-ZORA calculation shows the possible NIR emission induced by the [FeCp(CO)2]- chromophore accomplishing the antenna effect that justifies the sensitization of the actinide complexes.

UR - http://www.scopus.com/inward/record.url?scp=84947996460&partnerID=8YFLogxK

U2 - 10.1039/c5dt03121d

DO - 10.1039/c5dt03121d

M3 - Article

C2 - 26523807

AN - SCOPUS:84947996460

SN - 1477-9226

VL - 44

SP - 20004

EP - 20010

JO - Dalton Transactions

JF - Dalton Transactions

IS - 46

ER -